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CN106565396B - The method of cycloaddition production aromatic hydrocarbons - Google Patents

The method of cycloaddition production aromatic hydrocarbons Download PDF

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CN106565396B
CN106565396B CN201510656885.5A CN201510656885A CN106565396B CN 106565396 B CN106565396 B CN 106565396B CN 201510656885 A CN201510656885 A CN 201510656885A CN 106565396 B CN106565396 B CN 106565396B
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cycloaddition
aromatic hydrocarbons
reaction
molecular sieve
production aromatic
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CN106565396A (en
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孔德金
埃德曼T
伊夫T
宋奇
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Priority to DE102016219809.2A priority patent/DE102016219809A1/en
Priority to KR1020160132372A priority patent/KR102366203B1/en
Priority to GB1617289.2A priority patent/GB2550000B/en
Priority to FR1659849A priority patent/FR3042189B1/en
Priority to CA2945115A priority patent/CA2945115A1/en
Priority to US15/291,989 priority patent/US10604455B2/en
Priority to JP2016200904A priority patent/JP6976679B2/en
Priority to BR102016023812-9A priority patent/BR102016023812B1/en
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    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
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Abstract

The present invention relates to a kind of methods of cycloaddition production aromatic hydrocarbons.The method includes contacting raw material with catalyst to generate the arene stream containing benzene, toluene or dimethylbenzene；Wherein, the raw material includes divinyl macromer and dienophile；The divinyl macromer has structure formula (I):In formula (I), R1And R2For hydrogen, optionally the C replaced1‑20Linear or branched alkyl group, the C optionally replaced2‑20Linear chain or branched chain alkenyl, the C optionally replaced2‑20Linear chain or branched chain alkynyl, the C optionally replaced3‑20Naphthenic base or the C optionally replaced6‑20Aryl；The dienophile is C2~C4Alcohol.This method can be used in the industrial production of non-fossil sources aromatic hydrocarbons.

Description

The method of cycloaddition production aromatic hydrocarbons
Technical field
The present invention relates to a kind of methods of cycloaddition production aromatic hydrocarbons, prepare benzene, toluene or dimethylbenzene more particularly to a kind of The method of light aromatics.
Background technique
Benzene, toluene and dimethylbenzene are important bulk chemical, are the important basic organic chemical industry raw materials of social development, Itself or process reproduction can derive multiple product chain, and product is widely used in polyester, chemical fibre, rubber, medicine and essence Numerous areas, the domestic consumption amounts such as refinement work reach up to ten million tons, have great influence to the national economic development.Wherein, benzene is A kind of basic petrochemical material of multipurpose can produce numerous products, including ethyl benzene/styrene, cumene/phenol derived from it etc. Deng.Paraxylene passes through terephthalic acid (TPA) (PTA) or diethyl terephthalate (DMT) mainly for the manufacture of terephthalic acid (TPA) Intermediate gathers cruel fiber such as polyethylene terephthalate (PET), resin and film for producing.These three types of aromatic hydrocarbons are allusion quotations The light aromatics of type, is abbreviated as BTX.
The production of BTX depends on non-renewable fossil resource both at home and abroad at present, such as can be by a catalyst will Petroleum is by adding the technical process such as hydrogen, reformation, aromatic hydrocarbons conversion and separation to obtain.But fossil resource reserves are limited and can not be again Natural disposition, so that more being seen with the cost that petroleum is main refining raw material production aromatic hydrocarbons surging.In addition, fossil resource continually develops benefit With a large amount of greenhouse gas emissions are generated, caused a series of environmental problems is on the rise, therefore develops from renewable resource road Line produces that aromatic hydrocarbons is significant and application value.
Biomass is the carbon resource that nature is widely present, the features such as because of its renewable performance, neutral carbon and rich reserves It has received widespread attention.The annual yield of global biomass is about 200,000,000,000 tons.From reproducible biomass resource system Have the extensive concern that widely applied aromatic hydrocarbon product causes scientific circles and industry.
The research for preparing aromatic hydrocarbons through biomass route developed in recent years makes some progress.Except through synthesizing gas circuit Outside the method for line, fermentative routes and sugared plateform molecules conversion, synthesis aromatic hydrocarbons can also be by biomass-based furan derivatives by urging Change conversion to obtain.Biomass-based furan derivatives as reaction substrate then can be by cellulose, glucose, fructose by turning It is obtained after change.Such as 2,5- dimethyl furan, the compound can then be reacted with ethylene, be further dehydrated, be can produce PX Equal aromatic hydrocarbons (Cycloaddition of Biomass-Derived Furans for Catalytic Production of Renewable p-Xylene, C.Luke Williams, Chun-Chih Chang, Phuong Do, Nima Nikbin, Stavros Caratzoulas,Dionisios G.Vlachos,Raul F.Lobo,Wei Fan,and Paul J.Dauenhauer, ACS Catal., 2012,2 (6), pp 935-939).Document CN102482177A is also disclosed to diformazan The carbohydrate pathway of benzene, 2,5- dimethyl furans are reacted in the presence of cycloaddition reaction condition and catalyst with ethylene and are produced Raw paraxylene.But the route there is PX low yield, reaction need the ethylene of elevated pressures the deficiencies of.Meanwhile ethylene Using consuming fossil resource, while also increasing the operation difficulty and danger coefficient of reaction unit, it is therefore necessary to develop base In complete biomass route, have higher yields and the low new PX synthetic method of security risk concurrently.
Summary of the invention
The present invention is intended to provide a kind of method of cycloaddition production aromatic hydrocarbons.For achieving the above object, the present invention takes Technical solution it is as follows: the method for a kind of cycloaddition production aromatic hydrocarbons, including contact raw material under the conditions of cycloaddition with catalyst Generate the arene stream containing benzene, toluene or dimethylbenzene；Wherein, the raw material includes divinyl macromer and dienophile；
The divinyl macromer has structure formula (I):
In formula (I), R1And R2For hydrogen, optionally the C replaced1-20Linear or branched alkyl group, the C optionally replaced2-20Straight chain or branch Alkenyl, the C optionally replaced2-20Linear chain or branched chain alkynyl, the C optionally replaced3-20Naphthenic base or the C optionally replaced6-20Virtue Base；
The dienophile is C2~C10Alcohol.
In above-mentioned technical proposal, it is preferable that in formula (I), R1And R2For hydrogen, optionally the C replaced1-5Linear or branched alkyl group, The C optionally replaced2-10Linear chain or branched chain alkenyl.It is highly preferred that R1And R2For hydrogen, optionally the C replaced1-3Linear or branched alkyl group., R1And R2It can be identical also not identical.
In above-mentioned technical proposal, it is preferable that the dienophile is C2~C4Alcohol.It is highly preferred that the dienophile is selected from At least one of ethyl alcohol, normal propyl alcohol, isopropanol or sec-butyl alcohol.
In above-mentioned technical proposal, it is preferable that the catalyst includes ZSM-5, ZSM-22, Y, beta, MCM-22 or MCM- At least one of 41 molecular sieves.It is highly preferred that the catalyst includes at least one of ZSM-5, Y, beta or MCM-41 Molecular sieve.The molecular sieve uses after can forming with binder.In the optional self-alumina of the binder or silica extremely Few one kind.Its forming method be known in the art.
In above-mentioned technical proposal, it is preferable that the silica alumina ratio SiO of ZSM-5 or ZSM-22 molecular sieve2/Al2O3=10~ 500；It is highly preferred that SiO2/Al2O3=15~200.
In above-mentioned technical proposal, it is preferable that the silica alumina ratio SiO of Y molecular sieve2/Al2O3=2~800；It is highly preferred that SiO2/Al2O3=3~50.
In above-mentioned technical proposal, it is preferable that the silica alumina ratio SiO of beta molecular sieve2/Al2O3=10~150；More preferably Ground, SiO2/Al2O3=15~65.
In above-mentioned technical proposal, it is preferable that the silica alumina ratio SiO of MCM-22 or MCM-41 molecular sieve2/Al2O3=20~ 250；It is highly preferred that SiO2/Al2O3=40~150.
In above-mentioned technical proposal, it is preferable that the molar ratio of divinyl macromer and dienophile is 0.1~10.
In above-mentioned technical proposal, it is preferable that the cycloaddition condition are as follows: 80~400 DEG C of reaction temperature, catalyst amount is The 0.1~300% of raw material weight, reaction atmosphere include the mixed gas of nitrogen, hydrogen, carbon dioxide and above-mentioned gas.
In above-mentioned technical proposal, it is preferable that the divinyl macromer comes from biological material.
In above-mentioned technical proposal, it is preferable that the divinyl macromer comes from xylitol, glucose, fructose, cellobiose, half fiber At least one of dimension element or lignin.
In above-mentioned technical proposal, it is preferable that the raw material is in bagasse, glucose, timber, corn stalk or straw straw At least one.
In above-mentioned technical proposal, it is preferable that the dimethylbenzene is paraxylene.
In the arene stream containing benzene, toluene or dimethylbenzene of the method for the present invention production, by weight percentage, BTX aromatic hydrocarbons The content of (benzene, toluene or dimethylbenzene) is 20~90%, remaining is non-aromatics and heavy aromatics.
As an embodiment of the invention, divinyl macromer raw material of the present invention is biomass-based furans chemical combination Object, such as furans, methylfuran, 2,5- dimethyl furan.Such furfuran compound can be by from a wealth of sources, rich reserves Biomass material obtains, can be with large scale preparation.For example, 2,5- dimethyl furans can be by glucose, fructose, cellulose and 5- The biomass such as hydroxymethylfurfural add hydrogen to obtain (Thananatthanachon T, Rauchfuss T by acid catalysis B.Efficient Production of the Liquid Fuel 2,5‐Dimethylfuran from Fructose Using Formic Acid as a Reagent[J].Angewandte Chemie,2010,122(37):6766-6768.； Huang Y B,Chen M Y,Yan L,et al.Nickel–Tungsten Carbide Catalysts for the Production of 2,5‐Dimethylfuran from Biomass‐Derived Molecules[J] .ChemSusChem,2014,7(4):1068-1072.)。
The method of the present invention contributes to a kind of variation route of biomass material production aromatic hydrocarbons, especially to from biomass original The furfuran compound of material has preferable conversion ratio, has preferable choosing to benzene,toluene,xylene product, especially paraxylene Selecting property.Using the method for the present invention, reaction pressure is low, under the self-generated pressure of system, the conversion ratio highest of divinyl macromer raw material It can reach 99%；The selectivity of paraxylene can reach 87%, achieve preferable technical effect.
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
It weighs 35g fructose and is dissolved in the fructose soln that water forms 35%, NaCl and 5 milliliter of 0.25mol/L of 2% mass is added HCl solution, be uniformly mixed, add 100 milliliters of butanol as extraction phase extraction product.The mixture is anti-at 180 DEG C It answers 10 minutes, keeps the constant rate of organic phase and water phase during the reaction.The product obtained after reaction is 5- hydroxyl first Base furfural.It is further 1.0h in the hydrogen and mass space velocity of 220 DEG C and 6 atmospheric pressure by the compound-1Under urged in RuCu/C Hydrogenation reaction is carried out in agent, after reaction isolated 2,5- dimethyl furan.
1 gram is weighed through the ZSM-5 catalyst for removing water 12 hours dry at 120 DEG C, group is 50 as 50 parts of silica alumina ratio ZSM-5 molecular sieve, 50 parts of alumina binder, reaction substrate be 20ml 2,5- dimethyl furan and 20ml ethyl alcohol, Before reaction, using N2Displacement 5 times is carried out to reactor, is reacted 4 hours at 300 DEG C later, reaction pressure is self-generated pressure.Instead After answering, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate 2, The conversion ratio of 5- dimethyl furan is 96%, and the selectivity of paraxylene PX is 85%, and reaction product composition is shown in Table 1.
Table 1
Component Non-aromatics Benzene Toluene Ethylbenzene Paraxylene Meta-xylene Ortho-xylene C9 aromatic C10 +Aromatic hydrocarbons
Composition/wt% 14 0 0 0 85 0 0 0 1
[embodiment 2]
1 gram is weighed through the MCM-41 catalyst for removing water 12 hours dry at 120 DEG C, group is 100 as 50 parts of silica alumina ratio MCM-41 molecular sieve, 50 parts of alumina binder, reaction substrate be 20ml 2,5- dimethyl furan+200ml ethyl alcohol, Before the reaction, using H2Displacement 5 times is carried out to reactor, holding gas pressure is 0.1MPa, and reaction 6 is small at 250 DEG C later When, reaction pressure is self-generated pressure.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography ties reaction Fruit carries out quantitative analysis.Reaction substrate 2, the selectivity that the conversion ratio of 5- dimethyl furan is 83%, PX are 78%, reaction product Composition is shown in Table 2.
Table 2
Component Non-aromatics Benzene Toluene Ethylbenzene Paraxylene Meta-xylene Ortho-xylene C9 aromatic C10 +Aromatic hydrocarbons
Composition/wt% 22 0 0 0 78 0 0 0 0
[embodiment 3]
50 grams of fructose are weighed, 60 milliliters of formic acid are added, in 150 DEG C of 2 hours of stirring after mixing.Obtained brown mixture It is cooled to room temperature, is diluted later using 150 milliliters of tetrahydrofuran, continuously adds 5 milliliters of sulfuric acid and 4 grams of Pd/C is urged Agent.Obtained mixture continues to stir 10 hours at 70 DEG C.Reaction solution is filtered later, is diluted with 200 milliliters of water, It is extracted 3 times using 170 milliliters of ether again, obtained extract liquor merges, revolving obtains 2,5- dimethyl furan.
1 gram is weighed through the Y catalyst for removing water 12 hours dry at 120 DEG C, group becomes 60 parts of silica alumina ratio as 6 Y molecule Sieve, 40 parts of alumina binder, reaction substrate are the ethyl alcohol of 2, the 5- dimethyl furan+100ml of 30ml and mixing for sec-butyl alcohol The mixed proportion of conjunction object, ethyl alcohol and sec-butyl alcohol is 9:1, before the reaction, using N2Displacement 5 times is carried out to reactor, later 340 It is reacted 6 hours at DEG C, reaction pressure is self-generated pressure.After reaction, qualitative analysis, color are carried out to reaction result using mass spectrum Spectrum carries out quantitative analysis to reaction result.Reaction substrate 2, the selectivity that the conversion ratio of 5- dimethyl furan is 96%, PX are 86%, reaction product composition is shown in Table 3.
Table 3
Component Non-aromatics Benzene Toluene Ethylbenzene Paraxylene Meta-xylene Ortho-xylene C9 aromatic C10 +Aromatic hydrocarbons
Composition/wt% 22 0 0 0 86 0 0 0 2
[embodiment 4]
1 gram is weighed through the Y catalyst for removing water 12 hours dry at 120 DEG C, group becomes 65 parts of silica alumina ratio as 70 Y molecule Sieve, 35 parts of alumina binder, reaction substrate are that the ethyl alcohol of 2, the 5- dimethyl furan+750ml of 150ml is adopted before the reaction Use N2Displacement 5 times is carried out to reactor, is reacted 8 hours at 180 DEG C later, reaction pressure is self-generated pressure.After reaction, Qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate 2,5- dimethyl The selectivity that the conversion ratio of furans is 99%, PX is 87%, and reaction product composition is shown in Table 4.
Table 4
Component Non-aromatics Benzene Toluene Ethylbenzene Paraxylene Meta-xylene Ortho-xylene C9 aromatic C10 +Aromatic hydrocarbons
Composition/wt% 13 0 0 0 87 0 0 0 0
[embodiment 5]
20 grams are weighed through the ZSM-5 catalyst for removing water 12 hours dry at 120 DEG C, group is 300 as 10 parts of silica alumina ratio ZSM-5 molecular sieve, 90 parts of alumina binder, reaction substrate be 40ml 2- methylfuran+40ml isopropanol, anti- Ying Qian, using N2Displacement 5 times is carried out to reactor, is reacted 6 hours at 350 DEG C later, reaction pressure is self-generated pressure.Reaction After, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate 2- first The conversion ratio of base furans is 93%, and the selectivity of dimethylbenzene is 78%, and reaction product composition is shown in Table 5.
Table 5
Component Non-aromatics Benzene Toluene Ethylbenzene Paraxylene Meta-xylene Ortho-xylene C9 aromatic C10 +Aromatic hydrocarbons
Composition/wt% 20 0 0 0 10 28 40 0 2
[embodiment 6]
1 gram is weighed through the MCM-22 catalyst for removing water 12 hours dry at 120 DEG C, group is 150 as 40 parts of silica alumina ratio MCM-22 molecular sieve, 60 parts of alumina binder, reaction substrate be 20ml 2- methylfuran+20ml isopropanol, Before reaction, using CO2Displacement 5 times is carried out to reactor, holding gas pressure is 5Mpa, it is reacted 26 hours at 100 DEG C later, Reaction pressure is self-generated pressure.After reaction, using mass spectrum to reaction result carry out qualitative analysis, chromatography to reaction result into Row quantitative analysis.The conversion ratio of reaction substrate 2- methylfuran is 95%, and the selectivity of dimethylbenzene is 83%, reaction product composition It is shown in Table 6.
Table 6
Component Non-aromatics Benzene Toluene Ethylbenzene Paraxylene Meta-xylene Ortho-xylene C9 aromatic C10 +Aromatic hydrocarbons
Composition/wt% 17 0 0 0 1 33 49 0 0
[embodiment 7]
1 gram is weighed through the Y catalyst for removing water 12 hours dry at 120 DEG C, group becomes 50 parts of silica alumina ratio as 25 Y molecule Sieve, 50 parts of alumina binder, reaction substrate is the isopropanol of the 2- methylfuran+4ml of 40ml, before the reaction, using N2 Displacement 5 times is carried out to reactor, is reacted 6 hours at 280 DEG C later, reaction pressure is self-generated pressure.After reaction, it uses Mass spectrum carries out qualitative analysis to reaction result, and chromatography carries out quantitative analysis to reaction result.The conversion ratio of reaction substrate isopropanol It is 91%, the selectivity of dimethylbenzene is 82%, and reaction product composition is shown in Table 7.
Table 7
Component Non-aromatics Benzene Toluene Ethylbenzene Paraxylene Meta-xylene Ortho-xylene C9 aromatic C10 +Aromatic hydrocarbons
Composition/wt% 18 0 0 0 8 26 48 0 0
[embodiment 8]
1 gram is weighed through the ZSM-5 catalyst for removing water 12 hours dry at 120 DEG C, group is 150 as 55 parts of silica alumina ratio ZSM-5 molecular sieve, 45 parts of alumina binder, reaction substrate are the isopropanol of the 2- methylfuran+40ml of 40ml, are being reacted Before, using N2Displacement 5 times is carried out to reactor, using the gaseous mixture of hydrogen and nitrogen equal proportion, holding gas pressure is 1Mpa, It is reacted 8 hours at 250 DEG C later, reaction pressure is self-generated pressure.After reaction, reaction result is determined using mass spectrum Property analysis, chromatography to reaction result carry out quantitative analysis.The conversion ratio of reaction substrate 2- methylfuran is 83%, the choosing of dimethylbenzene Selecting property is 78%, and reaction product composition is shown in Table 8.
Table 8
Component Non-aromatics Benzene Toluene Ethylbenzene Paraxylene Meta-xylene Ortho-xylene C9 aromatic C10 +Aromatic hydrocarbons
Composition/wt% 22 0 0 0 4 27 47 0 0
[embodiment 9]
2 grams are weighed through the ZSM-5 catalyst for removing water 12 hours dry at 120 DEG C, group is 500 as 60 parts of silica alumina ratio ZSM-5 molecular sieve, 40 parts of alumina binder, reaction substrate are ethyl alcohol+sec-butyl alcohol mixing of the furans+100ml of 40ml Object, ethyl alcohol and sec-butyl alcohol mixed proportion are 1:1, before the reaction, using N2Displacement 5 times is carried out to reactor, later at 400 DEG C Reaction 6 hours, reaction pressure is self-generated pressure.After reaction, qualitative analysis, chromatography pair are carried out to reaction result using mass spectrum Reaction result carries out quantitative analysis.The selectivity that reaction substrate furans conversion ratio is 81%, BTX (including ethylbenzene) is 83%, instead Product composition is answered to be shown in Table 9.
Table 9
Component Non-aromatics Benzene Toluene Ethylbenzene Paraxylene Meta-xylene Ortho-xylene C9 aromatic C10 +Aromatic hydrocarbons
Composition/wt% 17 50 0 13 0 0 20 0 0
[embodiment 10]
36 grams of fructose are weighed, 50 milliliters of formic acid are added, 150 DEG C of 2 hours of stirring again after mixing.Obtained brown mixture It is cooled to room temperature, is diluted later using 100 milliliters of tetrahydrofuran, continuously adds 4 milliliters of sulfuric acid and the Pd/C of 4g is urged Agent.Obtained mixture continues to stir 10 hours at 70 DEG C.Reaction solution is filtered later, is diluted with 150 milliliters of water, It is extracted 3 times using 150 milliliters of ether again, obtained extract liquor merges and rotates to obtain 2,5- dimethyl furan.
2 grams are weighed through the beta catalyst for removing water 12 hours dry at 120 DEG C, group is 30 as 50 parts of silica alumina ratio Beta molecular sieve, 50 parts of alumina binder, reaction substrate is the ethyl alcohol of 2, the 5- dimethyl furan+40ml of 40ml, anti- Ying Qian, using N2Displacement 5 times is carried out to reactor, is reacted 5 hours at 300 DEG C later, reaction pressure is self-generated pressure.Reaction After, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate 2,5- The selectivity that the conversion ratio of dimethyl furan is 92%, PX is 78%, and reaction product composition is shown in Table 10.
Table 10
Component Non-aromatics Benzene Toluene Ethylbenzene Paraxylene Meta-xylene Ortho-xylene C9 aromatic C10 +Aromatic hydrocarbons
Composition/wt% 22 0 0 0 78 0 0 0 0
[embodiment 11]
1 gram is weighed through the beta catalyst for removing water 12 hours dry at 120 DEG C, group is 100 as 40 parts of silica alumina ratio Beta molecular sieve, 60 parts of alumina binder, reaction substrate is the ethyl alcohol of 2, the 5- dimethyl furan+20ml of 20ml, anti- Ying Qian, using N2Displacement 5 times is carried out to reactor, is reacted 6 hours at 250 DEG C later, reaction pressure is self-generated pressure.Reaction After, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate 2,5- The selectivity that the conversion ratio of dimethyl furan is 87%, PX is 81%, and reaction product composition is shown in Table 11.
Table 11
Component Non-aromatics Benzene Toluene Ethylbenzene Paraxylene Meta-xylene Ortho-xylene C9 aromatic C10 +Aromatic hydrocarbons
Composition/wt% 19 0 0 0 81 0 0 0 0
[embodiment 12]
2 grams are weighed through the MCM-41 catalyst for removing water 12 hours dry at 120 DEG C, group is 50 as 50 parts of silica alumina ratio The molecular sieve of MCM-41,50 parts of alumina binder, reaction substrate are the ethyl alcohol of 2, the 5- dimethyl furan+15ml of 30ml, Before the reaction, using N2Displacement 5 times is carried out to reactor, is reacted 6 hours at 300 DEG C later, reaction pressure is self-generated pressure. After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate The selectivity that the conversion ratio of ethyl alcohol is 89%, PX is 82%, and reaction product composition is shown in Table 12.
Table 12
Component Non-aromatics Benzene Toluene Ethylbenzene Paraxylene Meta-xylene Ortho-xylene C9 aromatic C10 +Aromatic hydrocarbons
Composition/wt% 18 0 0 0 82 0 0 0 0
[embodiment 13]
1.5 grams are weighed through the MCM-22 catalyst for removing water 12 hours dry at 120 DEG C, group is 70 as 50 parts of silica alumina ratio MCM-22 molecular sieve, 50 parts of alumina binder, reaction substrate be 80ml 2,5- dimethyl furan+20ml ethyl alcohol, Before the reaction, using N2Displacement 5 times is carried out to reactor, is reacted 3 hours at 330 DEG C later, reaction pressure is self-generated pressure. After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate The selectivity that the conversion ratio of ethyl alcohol is 83%, PX is 85%, and reaction product composition is shown in Table 13.
Table 13
Component Non-aromatics Benzene Toluene Ethylbenzene Paraxylene Meta-xylene Ortho-xylene C9 aromatic C10 +Aromatic hydrocarbons
Composition/wt% 15 0 0 0 85 0 0 0 0
[embodiment 14]
1 gram is weighed through the MCM-41 catalyst for removing water 12 hours dry at 120 DEG C, group is 150 as 50 parts of silica alumina ratio MCM-41 molecular sieve, 50 parts of alumina binder, reaction substrate be 20ml 2,5- dimethyl furan+100ml ethyl alcohol, Before the reaction, using N2Displacement 5 times is carried out to reactor, is reacted 5 hours at 280 DEG C later, reaction pressure is self-generated pressure. After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate The selectivity that the conversion ratio of 2,5- dimethyl furans is 86%, PX is 76%, and reaction product composition is shown in Table 14.
Table 14
Component Non-aromatics Benzene Toluene Ethylbenzene Paraxylene Meta-xylene Ortho-xylene C9 aromatic C10 +Aromatic hydrocarbons
Composition/wt% 24 0 0 0 76 0 0 0 0
[comparative example 1]
1 gram is weighed through the MCM-41 catalyst for removing water 12 hours dry at 120 DEG C, group is 150 as 50 parts of silica alumina ratio MCM-41 molecular sieve, 50 parts of alumina binder, reaction substrate be 20ml 2,5- dimethyl furan be dissolved in 20mL positive heptan Alkane carries out displacement 3 times to reactor using nitrogen, is then charged with 3MPa ethylene, reaction 5 is small at 280 DEG C later before the reaction When.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction Substrate 2, the selectivity that the conversion ratio of 5- dimethyl furan is 54%, PX are 48%, and reaction product composition is shown in Table 15.
Table 15
Component Non-aromatics Benzene Toluene Ethylbenzene Paraxylene Meta-xylene Ortho-xylene C9 aromatic C10 +Aromatic hydrocarbons
Composition/wt% 52 0 0 0 48 0 0 0 0
Table 16

Claims (14)

1. a kind of method of cycloaddition production aromatic hydrocarbons, including make raw material contact under the conditions of cycloaddition with catalyst generation contain benzene, The arene stream of toluene or dimethylbenzene；Wherein, the raw material includes divinyl macromer and dienophile；
The divinyl macromer has structure formula (I):
In formula (I), R1And R2For hydrogen, optionally the C replaced1-20Linear or branched alkyl group, the C optionally replaced2-20Linear chain or branched chain alkene Base, the C optionally replaced2-20Linear chain or branched chain alkynyl, the C optionally replaced3-20Naphthenic base or the C optionally replaced6-20Aryl；
The dienophile is C2~C10Alcohol；
The catalyst be molecular sieve catalyst, wherein the molecular sieve be selected from ZSM-5, ZSM-22, Y, beta, MCM-22 or At least one of MCM-41.
2. the method for cycloaddition production aromatic hydrocarbons according to claim 1, it is characterised in that in formula (I), R1And R2For hydrogen, optionally Substituted C1-5Linear or branched alkyl group, the C optionally replaced2-10Linear chain or branched chain alkenyl.
3. the method for cycloaddition production aromatic hydrocarbons according to claim 2, it is characterised in that in formula (I), R1And R2For hydrogen, optionally Substituted C1-3Linear or branched alkyl group.
4. the method for cycloaddition production aromatic hydrocarbons according to claim 1, it is characterised in that the dienophile is C2~C4Alcohol.
5. the method for cycloaddition production aromatic hydrocarbons according to claim 4, it is characterised in that the dienophile is selected from ethyl alcohol, just At least one of propyl alcohol, isopropanol or sec-butyl alcohol.
6. according to claim 1 cycloaddition production aromatic hydrocarbons method, it is characterised in that the molecular sieve be selected from ZSM-5, Y, At least one of beta or MCM-41.
7. the method for cycloaddition production aromatic hydrocarbons according to claim 1, it is characterised in that the silicon of ZSM-5 or ZSM-22 molecular sieve Al mole ratio SiO2/Al2O3=10~500；The silica alumina ratio SiO of Y molecular sieve2/Al2O3=2~800；Beta molecular sieve Silica alumina ratio SiO2/Al2O3=10~150；The silica alumina ratio SiO of MCM-22 or MCM-41 molecular sieve2/Al2O3=20~ 250。
8. the method for cycloaddition production aromatic hydrocarbons according to claim 7, it is characterised in that the silicon of ZSM-5 or ZSM-22 molecular sieve Al mole ratio SiO2/Al2O3=15~200；The silica alumina ratio SiO of Y molecular sieve2/Al2O3=3~50；The silicon of beta molecular sieve Al mole ratio SiO2/Al2O3=15~65；The silica alumina ratio SiO of MCM-22 or MCM-41 molecular sieve2/Al2O3=40~150.
9. the method for cycloaddition production aromatic hydrocarbons according to claim 1, it is characterised in that mole of divinyl macromer and dienophile Than being 0.1~10.
10. the method for cycloaddition production aromatic hydrocarbons according to claim 1, it is characterised in that the cycloaddition condition are as follows: reaction 80~400 DEG C of temperature, catalyst amount is the 0.1~300% of raw material weight, and reaction atmosphere includes nitrogen, hydrogen, carbon dioxide And the mixed gas of above-mentioned gas.
11. the method for cycloaddition production aromatic hydrocarbons according to claim 1, it is characterised in that the divinyl macromer comes from biological material Material.
12. according to claim 1 cycloaddition production aromatic hydrocarbons method, it is characterised in that the divinyl macromer from xylitol, At least one of glucose, fructose, cellobiose, hemicellulose or lignin.
13. the method for cycloaddition production aromatic hydrocarbons according to claim 1, it is characterised in that the raw material comes from bagasse, Portugal At least one of grape sugar, timber, corn stalk or straw straw.
14. the method for cycloaddition production aromatic hydrocarbons according to claim 1, it is characterised in that the dimethylbenzene is paraxylene.
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